Hydrocarbon conversion process



United States Patent 3 156 737 HYDRQQCAREQN ZCQEQVERSEON PROCESS Louis C. Gutberlet, Cedar Lake, ind, assiguor to Stand- ?rd @ii tlompany, @hicago, 1311., a corporation of No Drawing. Filed Mar. 15, 1961, er. No. 95,827 16 Claims. (Ql. 260--6ti3.65)

This invention relates to hydrocarbon conversion catalysts and more particularly it relates to the production of branched chain paraffinic hydrocarbons. Still further, the invention relates to a method of producing high yields of isoparatlins from normal olefins or from hydrocarbon mixtures containing substantial amounts of normal olefins by contacting such olefinic materials with particular catalyst having critically balanced isomerization and hydrogenation activities, the balance in the catalyst activities being achieved by the incorporation in the catalyst of small amounts of the normally solid elements of Group VA of the Periodic Table.

Light isoparafiins, i.e., within the gasoline boiling range, have markedly higher leaded motor octane ratings than either olefins of the same carbon number or the corresponding normal paraifins. Also, there has evidenced a trend to limit the amount of olefins in gasoline, at least in certain geographic areas. Therefore, there is a definite advantage for saturating the olefins in rafinery streams such as light cracked naphtha, and a further advange results from converting the normal hydrocarbons in such streams to branched chain hydrocarbons.

Prior art hydrocarbon conversion processes are known wherein multifunctional catalysts are employed to promote simultaneous reactions, such as cracking, hydrogenation, cyclization, isomerization, etc. Many of these catalysts are known to lose their catalytic effectiveness rapidly, because of the presence of such catalyst poisons as arsenic, sulfur and like. Notable among these are the platinum type reforming catalysts which are known to be rapidly poised by only small amounts of arsensic in the eed contacting the catalyst.

Also, processes are known in the art for converting normal olefinic hydrocarbons, to isoparafiins. However, these prior art processes, because of their nature, have not succeeded in producing high yields of isoparaffins, and the resulting product has had a low iso to normal (i/ n) paraiiin ratio. It is believed that in such processes the relatively rapid straight chain hydrogenation reaction competes with the concurrent isomerization reaction to lower the yield of isoparatfin to less than that which would result from either the straight isomerization of the parafiin or of the olefin in the absence of the concurrent hydrogenation reaction. The isoparaffin yield from these prior processes, of course, varies with temperature. However, none are capable of achieving greater than paraifin isomerization equilibrium yields of isoparaflins under comparable temperature conditions. i

It has now been discovered that extremely high yields of isoparafiins are produced in a hydrocarbon conversion process which comprises contacting an olefinic hydrocarbon with a catalyst having a hydrogenation activity and an isomerizatiou activity in a reaction zone in the presence of a hydrogen-affording gas under elevated pressure and at a temperature in the range of about 400 F. to 750 B, said catalyst comprising a metallic hydrogenation component, a solid acidic component, and an activity control-aiiording substance comprising a normally solid element of Group VA of the Periodic Table, particularly arsenic and antimony, whereby there is provided a converted paraffinic branched chain product containing more branched chain paraffins than the parafiin isomerization equilibrium amount at the operating temperature.

In one preferred embodiment of the invention, the

3,156,737 Patented Nov. 10, 1964 process employs a catalyst comprising an arsenided nickel on silica-alumina catalyst, the silica-alumina preferably containing about S'to 40 weight percent alumina.

In another preferred form, the process of the invention employs an arsenided platinum on silica-alumina catalyst, the silica-alumina preferably containing about 5 to 40 weight percent alumina.

In another aspect, the invention provides a hydrocarbon conversion process comprising contacting an olefinic hydrocarbon with a catalyst in a reaction zone in the presence of a hydrogen-affording gas under elevated pressure and at a temperature in the range of about 400 F. to 750 B, said catalyst comprising a metallic hydrogenation component, a solid acidic component, and an activity control-affording substance comprising a normally solid element of Group VA of the leriodic Table, whereby there is provided a converted parafiinic branched chain product containing more branched chain paraflins than the paraffin isomerization equilibrium amount at the operating temperature, subsequently purging said hydrocarbon-contacted catalyst of combustibles, contacting said purged catalyst with oxygen-containing gas at elevated temperature to oxidize accumulated carbonaceous deposits on said catalyst and contacting said oxygen-contacted catalyst with hydrogen-containing gas at elevated temperature to reduce metallic oxides resulting from contact with said oxygen-containing gas, said elevated temperatures being controlled to prevent permanent damage to said catalyst.

It is to be understood that the activity control-affording substances described herein can be incorporated in the catalyst during its manufacture and/ or at any time during its use. Further, the term normally solid elements of Group VA of the Periodic Table is to be understood to be those elements of the Periodic Table (from College Chemistry (2nd ed), by Paul R. Frey, Prenticelall, Inc, 1958), which elements are solid at room temperature and atmospheric pressure. These elements may be present in the catalyst in various chemical combinations and/ or in elemental form.

In the process of the invention, an olefinic hydrocarbon stream, which may be a substantially pure olefin or a hydrocarbon mixture having substantial olefin content, preferably about 50 percent or more olefins, is selected as a feed. Refinery streams particularly suitable as feed stocks for the process are light cracked naphthas boiling in the range from about 20 F. to about 350 F. and containing substantial quantities of normal olefins having a carbon number distribution in the range from about C to C Advantageously, the olefins to be converted fall within the C -C range, and most preferably are C and C olefins. The olefin feed stock may be derived from petroleum, shale, gilsonite or other such organic materials.

The olefinic feed is introduced into a reaction zone where it is contacted with the catalyst in the presence of at least sufficient hydrogen for olefin saturation. The operation may be liquid phase, vapor phase, or mixed liquid-vapor phase. Advantageously, a hydrogenrich gas such as substantially pure hydrogen, catalytic reformer make-gas or other gas streams containing sufiicient hydrogen for olefin saturation is introduced into the reaction zone with the feed. The minimum amount of hydrogen required will be the stoichiometric amount required for olefin saturation, and the amount of hydrogen will vary according to the nature of the feed stock. Preferably, an excess of hydrogen is employed, which in practice will usually be at least about 1500 s.c.f. per barrel of olefinic feed. Larger excesses of hydrogen or inert gases may be employed to reduce olefin partial pressure to increase the i/ n paraffin ratio of the converted product.

The reaction zone is operated under conditions pro- U moting the isomerization-hydrogenation of olefins to isoparaiiins. A superatmospheric pressure is employed, which pressure can range up to 3(300 p.s.i.g. or more, but preferably is in the range of about G to 1560 p.s.i.g. An elevated temperature is employed in the catalyst bed, which temperature typically is in the range of about 400 F. to 750 F., and preferably is about 450 F. to 650 F. Catalyst activities, the nature of the material charged to the reaction zone, pressure and other operating variables will affect the selection of the operating temperature. Liquid hourly space velocities (LHSV) of from about 0.1 to 50 volumes of hydrocarbon (as liquid) per hour per volume of catalyst are employed, most generally about 0.1 to 10 LHSV, and with a preferred rate being about 0.5 to 3 LHSV.

The catalyst employed in the present invention possesses isomerization activities and hydrogenation activities, with tiese activities being so balanced with respect to one another to provide remarkably high yields of isoparafiins in the converted product. Metallic hydrogenation catalyst such as the metals of Group Vlll of the Periodic Table, particularly nickel, platinum, palladium and cobalt, preferably are supported on an acidic isomerization catalyst such as silica-alumina. In a prefe ed embodiment of the invention, the metallic hydrogenation component supported on silica-alumina is impregnated with arsenic to arsenide the catalyst and thereby control the hydrogenation activity to a level relative to the isomerization activity which permits a converted product having a high i/n paraffin ratio. With a properly balanced catalyst product i/n paraffin ratios as high as about may be achieved with yields of isoparai'lins as high as about 959 While a supported type catalyst is preferred, other catalyst forms may be employed, such as a catalyst wherein the various components are co-precipitated from a sol, etc.

The amount of the hydrogenation component incorporated in the cateuyst can vary over a wide range, with the amount being selected to provide the desired catalyst activity. For example, large amounts of nickel, e.g., up to about 30 wei ht percent can be employed, and as little as about 0.1 weight percent is also effective, with about 0.5 to 5 weight percent nickel being prererred. Typically, about 0.1 to 2 weight ercent platinum has likewise been found to be very effective and preferably about 0.1 to 1 Weight percent platinum is employed.

The solid acidic component of the catalyst can be a naturally occurring mineral such as montmorillonite clay, a synthetic silica-alumina, or a combination of these. in general this component must provide suiiicient acidity to promote the skeletal isomerization of olelins, and a porous, high surface area material of about lQC f-tl-O square meters per gram is employed. Preferably, artific al aluminosilicate, such as one of the commercially available silicaalumina cracking catalysts is utilized as a support. These cracking catalysts are made by co-pre ltating alumina and silica sols. The alumina portion of the support may vary from about 5 to about 40 weight percent. Both the commercially available hi h-alumina silica-alumina cracking catalysts containing about 2G-30 Weight percent A1 0 and the low alumina material containing about 10-15 weight percent A1 0 are effective as a component of the present catalyst.

It is necessary to incorporate sufiicient of the aforementioned Group VA elements in the catalyst to properly balance the catalyst activities so that a favorably rapid over-all rate of olefin isomerization compared to the overall rate of hydrogenation is provided. it is critical that sufficient activity control-affording material be employed to achieve the desired catalyst activity control, while avoiding the use of eircessive amounts of modifying elements so as to reduce the hydrogenation activity to a to provide a saturated product. Norlevel insufiicient mally, only small amounts of arsenic, phosphorous, antimony and/or bismuth are required to properly balance the catalyst and these activity modifying elements can be employed either singly or in combination. The total amount of the activity control-atlording substance rc quired will be dependent upon the total amount or the particular hydrogenation metal incorporated in the catalyst and upon its chemical form, i.e., arsenic may be present as either the arsenide or a sub-arscnide. Typically, a 5 percent nickel-catalyst having from about 0.5 to 6.4 Weight percent added arsenic may be employed. Generally no more than one mole of activity controlailording substance per mole of hydrogenation metal is required in the catalyst, although greater amounts may be employed as long as the desired catalyst activity is maintained. About 0.91 to 5 moles of phosphorus, arsenic, antimony and/or bismuth may be incorporated in the catalyst, however, about 0.1 to 1 mole of such elements per mole of hydrogenation metal preferably is employed.

Preferably, the Group VA elem-at is incorporated in the catalyst during, its manufacture. For example, a nickel on silica-alumina catalyst base can be impregnated with a solution of an organic compound, including aryl or alkyl substituted organo-met "cs, such as triphenyl arsine, tricresyl phosphite, triphenyi stibine, etc., the solvent evaporated and the organic compound reduce to leave a deposit on the base. Also, the catalyst base can be impregnated with inorganic compounds, including acids, an'unonium salts, nitrates, h 3, etc., or" the normally solid Group VA elements sucn as arsenic trioxide in an ammoniacal soluti. with subsequent drying, calcination and reduction of t catalyst by hydrogen. Also, normally solid Group VA elements may be introduced into the reaction zone to contact the catalyst base in situ and thereby balance the catalyst activity. Typically, organic compounds of arsenic may be introduced into the reaction zone with the fcec so that the arsenic is made available to the catalyst.

A particular advantage resulting from the use of the above-described catalysts in the process of the invention is the fact that once the arsenic, antimony, etc. are incorporated in the catalysts there is little tendency under the conditions of the process for the arsenic group elements of the catalyst to be removed and thereby lose control of the critical activity balance. Consequently, it is not necessary under normal conditions to maintain activity control-affording material in the feed.

After a period of operation wherein the catalyst is contacted with the hydrocarbon feed the catalyst activity declines and carbonaceous deposits accumulate on the catalyst. Olefin breakthrough, i.e., the ap earance or" unsaturates in the reactor effluent, indicates t effective on-stream cycle length for the catalyst. When olefin breakthrough occurs, the catalyst can be regenerated to restore its ac Ivity to permit the production of a saturated product having a high i/n parailin ratio again.

The following sequence of steps typifies a regeneration technique which has been found to be very effective in restoring the activities of the deactivated catalyst employed in the present process:

(1) The catalyst bed and reaction zone are purged of combustible 1 aterials such as hydrocarbons, and hydrogen, by passing inert gas such as nitrogen, carbon dioxide, flue gas, etc, through the catalyst bed. Advantageously, this inert gas purge is carried out at atmospheric pressure, but higher pressure may be employed. Preferably, the temperature of the catalyst bed is adjusted to the burnofi temperature during th period or" purging by externally heating the catalyst bed or by passing a heated inert gas into the bed. Typically, a 600-650 F. operating temperature is employed and while purging the catalyst bed temperature is raised to a temperature in the range of about 750-1060" E, preferably about 850 F, sufficient to burn oil the carbonaceous deposits on the catalyst.

(2) After the combustibles are purged from the catalyst bed and the reactor to a sufficiently low level, an oxygencontaining gas is contacted with the catalyst at a controlled rate to oxidize the carbonaceous deposits. mainly coke, on the catalyst. The burnofl rate is limited by the oxygen supplied, and the catalyst bed during the burnotf period must not be permitted to overheat so as to cause permanent catalyst damage by sintering any of the catalyst components, reducing the surface area or causing harmful crystalline phase changes. A maximum temperature of about 1000 F. is permissible with a nickel on silica-alumina catalyst, although with other metals such as platinum, higher temperatures may be employed. However, the burnofi has been carried out very satisfactorily by employing, first, a diluted oxygen-containing gas such as about 2-20% oxygen in nitrogen and preferably a 2% oxygen in nitrogen gas at 750l000 F. to burnoff most of the coke, followed by contacting the catalyst with atmospheric air at 850 F. to oxidize any remaining carbonaceous deposits.

(3) Following the burnoit, it is preferred to again purge the catalyst bed, as with an inert gas such as described above to remove any remaining oxygen, and the catalyst bed temperature preferably is reduced to the process operating temperature during this period.

(4) Then, the catalyst is contacted with a hydrogencontaining gas. Metal oxides resulting from contact with the oxygen-containing gas during the burnoff period are reduced by the hydrogen. In this step, hydrogen, hydrogen-rich recycle gas from the present process or other processes such as catalytic reforming, and similar gas streams containing sufiicient available hydrogen may be uailized. Preferably, the hydrogen contacting step is carried out at approximately the process operating temperature and pressure, but other conditions operative for the reduction may be employed.

After regenerating catalysts employed in the present process as described above, the regenerated catalysts were found to possess their original level of activities and to be capable of permitting a fully saturated product with a high yield of isoparaflins.

The following examples are given as being illustrative of the operation of the process of the invention. However, it is to be understood that these examples are given by way of illustration only, and do not serve in any way to limit the scope of the present invention.

COMPARISON TEST lowing composition:

Wt. percen C .3 iCA 4.5 I1 3; .9 1c, 34.2 nC 51.1 C 9.0

As seen from the above analysis, the i/nC parafiin ratio was less than 1 and the isoparafin yield was very low.

Example I A catalyst was prepared comprising 5 weight percent nickel and 2.5 weight percent arsenic on silica-alumina support containing about 25 Weight percent alumina. In the preparation of the catalyst, a silica-alumina cracking catalyst was impregnated with an aqueous solution of nickel acetate. The impregnated material was dried at about 400 F., mixed with 4 percent Sterotex (hydrogenated coconut oil), pelleted to As size and calcined for 6 hours at 1000 P. Then the calcined catalyst was crushed and impregnated with a solution of triphenyl arsine in normal heptane. The heptane was evaporated and the arsenous catalyst was placed in a tube type reactor where it was treated with flowing hydrogen at atmospheric pressure at 850 F. to decompose the arsine to arsenic.

The final catalyst contained about 2.5 weight percent arsenic. This catalyst was charged to a reactor and diluted, 3 cc. to 12 cc. of 20-48 mesh quartz. The catalyst was contacted with normal pentene which contained about 2.4% normal pentane at 1000 p.s.i.g., 612 F, 10 Li-ISV and 11 M s.c.f. of hydrogen per barrel of olefin. The reactor efiluent was analyzed by gas chromatography and found to contain the following:

Product, wt. percent:

As noted from the above data, the arsenous catalyst was effective in producing a high i/nC paraffin ratio with a high yield of isoparaffins.

Example II A 5 percent nickel on silica-alumina catalyst was prepared as described in Example I above. Subsequently, the arsenided catalyst was contacted with a catalytic debutanized naphtha. This naphtha contained about 7 weight percent C s, 48 weight percent C s and 45 weight percent C s through C s.

This feed stock was contacted with the catalyst at 250 p.s.i.g., 635 F., 1.5 LHSV and a 9 to 1 H to hydrocarbon mole ratio. After 14 hours olefin breakthrough occurred, indicating the effective cycle length of the catalyst. The i/nC parafin ratio of the reactor effluent was 10 to 1. About 5 percent C s through C s were produced in the process.

The compositions of the C fraction of the Cat. DAN and of the 99+% saturated product is shown below:

When the olefin breakthrough occurred, the feed and the hydrogen to the reactor were stopped and the catalyst bed and reactor were purged with nitrogen at atmospheric pressure while the catalyst bed temperature was raised to 850 F. This purging was continued until the reactor was rid of hydrocarbons and hydrogen.

The nitrogen purge was then followed by a burnoif with 2 percent oxygen in nitrogen at 850 F. and atmospheric pressure for approximately 3 hours. During this period of time, the gas flow rate was about 3 cubic feet per hour.

Following the 2 percent oxygen burnott, the catalyst was contacted with air at 850 F. and atmospheric pressure for about 3 hours, during which the gas flow rate was maintained at about 3 cubic feet per hour.

Following the air burnotr', the reactor was purged with nitrogen at a flow rate of 3 cubic feet per hour for about 1 hour. During this period, the catalyst bed temperature was lowered to about 650 F.

After ridding the reactor of oxygen-containing gases, the catalyst was contacted with hydrogen at 250 p.s.i.g. and about 650 to 750 F.

Following the hydrogen reducti n step, he oil processing cycle was repeated at the con .tlons stated above using some feed stock. The reactor efiluent from the regenerated catalyst bed was observed to have an i/nC par n ratio of about 10 to 1. This processing cycle was again continued for 14 hours at which time the catalyst was regenerated as described above.

The above described cycles of oil processing an eration were conducted at least 17 times. After generation and during each processing cycle, the catalyst was found to possess a high activity and to function as described, with the reactor effluent being fully saturated and having an i/nC paraffin ratio of about it) to l.

The following octane results are a indication of the octane improvement which may be obtained by the present process:

Example 111' n catal st was repared A 1% platinum on SlllCZl-Ztllll silic "alumina cracking by impregnating a 25-pcrcent catalyst with chloroplatinic acid, mg at about 400 F. and mixing 4 percent Sterote This composite was then pelleted and calcined for 6 hours at l000 Following this the composite was impregnated with triphcnyl arsine in normal heptane as described above to give 0.8 weight percent arsenic on the catalyst, after which it was reduced in flowing hydrogen at 750 F. The catalyst was placed in a tube reactor and diluted, 20 cc. to cc. of deactivated alumina spheres. Then the catalyst was tacted with pentenc-Z at 650 F, 1.5 LHSV, 250 p.s.i.g. and a 10 to 1 hydrogen to hydrocarbon mole ratio. reactor efiluent contained a small amount of olefin indicating incomplete saturation. The i/nC par-shin ratio of the reactor eilluent was 11.5.

Example I V Example V A 5% niclel on 25% alumina silica-alumina cata 'st base was prepared as described in Example I, and l% arsenic was incorporated in the catalyst by impregnating the base with a 25% ammoniacal solution of arsenic trioxide, drying and calcining at 1000" F. The ar enided catalyst was contacted with pentene-Z at 1000 p.s.i.g., 10 to 1 hydrogen to hydrocarbon mole ratio, 10 .e lSV and about 580 F. The resulting product was 85.4% saturated and the i/nC parafiin ratio was 10.

Example VI A catalyst was prepared and run as described in E7;- ample V, except that 1% antimony was incorporated in the catalyst in lieu of the arsenic by impregnating the catalyst base with an aqueous solution of antimony trichloride. The reactor efiluent was saturated and the i/nC paraffin ratio was 5R1.

Example VII A catalyst was prepared and run as described in Example V, except that 1% bismuth was incorporated in the catalyst in 11611 of the arsenic by impregnating the cata- Q to lyst based with an ethanoiie solution of bismuth nitrate. The reactor eflluent was about 50% saturated and the i/nC paratfin ratio was 7.1.

From the foregoing examples, it is seen that the process of the present invention as described above is capable of producing remarkably high yields of isoparatfins and that the catalysts are readily regenerated after they become deactivated.

It is to be understood that the terms arsenided, antimonided, bismuthidcd, etc. as used herein refer to the incorporation of arsenic, antimony, bismuth, etc., respectively, in the catalyst compositions to cllect the desired balance of catalyst activities.

Further, the hereinbefore described catalysts have been found to be effective hydrocarbon conversio catalysts for the hydrocracking of a hydrocarbon distillate boiling in the range of about 300 F. to 800 F.

What is claimed is:

1. A process for the production of branched. chain parailinic hydrocarbons which process comprises contacting an olefinic hydrocarbon with a catalyst in a reaction zone in the presence of a hydrogen-affording g. 5 under elevated pressure and at a temperature in a range of about 400 F. to 750 B, said catalyst comprising a metallic hydrogenation component, a solid acidic component, and an activity control-affording substance comp ing a normally solid element of Group VA 0f the Periodic Table, whereby there is provided a converted paraihnfc branched chain product containing more branched chain psratlins than the parailin isomerization equilibrium amount at the operating temperature.

2. A process for the production of branched chain paraffinic hydrocarbons which process comprises contacting an olefinic hydrocarbon with a catalyst in a reaction zone in the presence of a hydrogen-affording gas under elevated pressure and at a temperature in a range of about 400 F. to 750 B, said catalyst comprising an element selected from the group consisting of the metals of Group Vii of the Periodic Table, a normally solid element of Group VA of the Periodic Table and silicaalumina, whereby there is provided a converted paratlinic branched chain product containing more branched chain paraffins than the paraflin isomerization equilibrium amount at the operating temperature.

3. A process for the production of branched chain paraffinic hydrocarbons which process comprises contacting an olefinic hydrocarbon with a catalyst in a rcac tion zone in the presence of an hydrogen-affording gas under elevated pressure and at a temperature in a range of about 400 F. to 700 B, said catalyst comprising a metallic hydrogenation component, a solid acidic component and an activity control-affording substance comprising a normally solid element of Group VA of the Periodic Table, whereby there is provided a converted paratlinic branched chain product containing more branched chain paraffins than the paraifin isomerization equilibrium amount at the operating temperature; subsequently, purging said hydrocarbon contacted catalyst of ccmbustibles; contacting said purged catalyst with an oxygen-containing gas at elevated temperature to oxidize accumulated carbonaceous deposits on said catalyst; and contacting said oxygen contacted catalyst with hydrogen-containing gas at elevated temperature to reduce the metallic oxides re sulting from contact with said oxygen-containing gas; said elevated temperatures being controlled to prevent permanent damage to said catalyst.

4. The process of claim 3 wherein said catalyst comprises a metal selected from Group VIII of the Periodic Table, silica-alumina and a normally solid element of Group VA of the Periodic Table.

5. The process of claim 3 wherein said catalyst comprises arsenided nickel on silica-alumina.

6. The process of claim 3 wherein said cat.lyst comprises arsenided platinum on silica-alumina.

7. A hydrocarbon conversion catalyst comprising a metallic hydrogenation component, a solid acidic component and from about 0.01 to 5.0 moles of an element selected from the group consisting of arsenic, antimony and bismuth per mole of the metal constituent of said hydrogenation component.

8. A process for the production of branched-chain paraffinic hydrocarbons which process comprises contacting a C -C olefinic hydrocarbon with a catalyst in a reaction zone in the presence of a hydrogen-affording gas at a temperature in the range of about 450 F. to 650 F, a pressure in the range of about 100 to 1500 p.s.i.g., a space velocity of about 0.1 to 10 volumes of oil per hour per volume of catalyst and a hydrogen to carbon ratio of at least about 1500 s.c.t. of hydrogen per barrel of olefin, said catalyst consisting essentially of an element selected from the group consisting of metals of Group VIII of the Periodic Table supported on a silica-alumina cracking catalyst base and from about 0.1 to 1 mole of an element selected from the group consisting of arsenic, antimony and bismuth per mole of said Group VIII metal.

9. A process for the production of branched chain parafiinic hydrocarbons which process comprises contacting an olefinic hydrocarbon with a catalyst in a reaction zone in the presence of a hydrogen-affording gas under elevated pressure and at a temperature in a range of about 400 F. to 750 F., said catalyst comprising arsenided nickel on silica-alumina, whereby there is provided a converted paraffinic branched chain product containing more branched chain paraffin-s than the parafiin isomerization equilibrium amount at he operating temperature.

10. The process of claim 9 wherein said silica-alumina contains about 5 to 40 weight percent alumina.

11. The process of claim 9 wherein said catalyst comprises about 0.1 to 30 weight percent nickel supported on said silica-alumina and from about 0.01 to 5 moles of arsenic per mole of nickel.

12. A process for the production of branched chain parafiinic hydrocarbons which process comprises contacting an olefinic hydrocarbon with a catalyst in a reaction zone in the presence of a hydrogen-affording gas under elevated pressure and at a temperature in a range of about 400 F. to 750 F., said catalyst comprising arsenided platinum n silica-alumina, whereby there is provided a converted paraflinic branched chain product containing 10 more branched chain parafiins than the parafiin isomerization equilibrium amount at the operating temperature.

13. The process of claim 12 wherein said silica-alumina contains about 5 to 40 Weight percent alumina.

14. The process of claim 12 wherein said catalyst comprises about 0.1 to 2 percent platinum supported on said silica-alumina and about 0.01 to 5 moles of arsenic per mole of platinum.

15. A process for the production of branched chain parafiinic hydrocarbons which process comprises contacting an olefinic hydrocarbon with a catalyst in a reaction zone in the presence of .a hydrogen-affording gas under elevated pressure and at a temperature in a range of about 400 F. to 750 15., said catalyst comprising antimonided nickel on silica-alumina, whereby there is provided a converted paraffinic branched chain product containing more branched chain parafiins than the parafiin isomerization equilibrium amount at the operating temperature.

16. A process for the production of branched chain paraffinic hydrocarbons which process comprises contacting an olefinic hydrocarbon with a catalyst in a reaction zone in the presence of a hydrogen-aflording gas under elevated pressure and at a temperature in a range of about 400 F. to 750 F. said catalyst comprising bismuthided nickel on silica-alumina, whereby there is provided a converted pa-rafiinic branched chain product containing more branched chain parafiins than the paraffin isomerization equilibrium amount at the operating temperature.

References Cited in the file of this patent UNITED STATES PATENTS 2,418,023 Frey Mar. 25, 1947 2,864,875 McKinley et a1 Dec. 16, 1958 2,926,207 Folkins et al. Feb. 23, 1960 2,987,486 Carr June 6, 1961 3,003,009 Gurd et al Oct. 3, 1961 OTHER REFERENCES Innes Catalysis, vol. I, Reinhold Publishing Corp. (1954), pages 299-314 (page 306 particularly relied upon).

Corson: Catalysis, vol. III, Reinhold Publishing Corp. (1955); pages 101-104.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No., 3 1565137 November m 1964 Louis C., Gutberlet It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column l line 27, for "refinery" read refinery line 39, for "poised" read poisoned column 5 line .2 for "deposits." read deposits column 6 in' the table of Example 2 under the heading "Product" the column should appear as shown below instead of as in the patent:

. w 9 Less than 1% (SEAL) Signed and sealed this 6th day of April 1965,

Attest:

ERNEST W. SWIDER' EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. A PROCESS FOR THE PRODUCTION OF BRANCHED CHAIN PARAFFINIC HYDROCARBONS WHICH PROCESS COMPRISES CONTACTING AN OLEFINIC HYDROCARBON WITH A CATALYST IN A REACTION ZONE IN THE PRESENCE OF A HYDROGEN-AFFOIRDING GAS UNDER ELEVATED PRESSURE AND AT A TEMPERATURE IN A RANGE OF ABOUT 400*F. TO 750*F., SAID CATALYST COMPRISING A METALLIC HYDROGENATION COMPONENT, A SOLID ACIDIC COMPONENT, AND AN ACTIVITY CONTROL-AFFORDING SUBSTANCE COMPRISING A NORMALLY SOLID ELEMENT OF GROUP VA OF THE PERIODIC TABLE, WHEREBY THERE IS PROVIDED A CONVERTED PARAFFINIC BRANCHED CHAIN PRODUCT CONTAINING MORE BRANCHED CHAIN PARAFFINS THAN THE PARAFFIN ISOMERIZATION EQUILLIBRIUM AMOUNT AT THE OPERATING TEMPERATURE. 